Abstract
Recently, biodiesel production using heterogeneous catalysts has been of great concern. However, simple separation of these catalysts from product mixtures is a problem of the process. In this study, series of magnetic KOH/Fe3O4@Al2O3 core–shell nanocatalysts were synthesized via the incipient wetness impregnation method and the effect of weight ratio of Fe3O4-to-Al2O3 (0.15–0.35) on the catalytic performance was assessed. The samples were characterized by XRD, FTIR, BET-BJH, VSM, SEM, TEM, and EDX analyses and their basicity was measured by the Hammett indicator method. The results revealed that although the magnetic KOH/Fe3O4@Al2O3 nanocatalyst with 25 wt% of Fe3O4 showed less activity as compared to those with 15 wt% of Fe3O4, it exhibited higher surface area and appropriate magnetic properties. The sample presented superparamagnetic properties with the magnetic strength of 1.25 emu/g that was simply recovered by using an external magnetic field. The nanocatalyst converted 98.8% of canola oil to biodiesel under reflux condition at the best operational conditions of 12 M ratio of methanol/oil, 4 wt% of catalyst and 6 h of reaction time. Moreover, the nanocatalyst showed high reusability such that it was reused several times without appreciable loss of its catalytic activity.
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References
Ahangaran F, Hassanzadeh A, Nouri S (2013) Surface modification of Fe3O4@SiO2 microsphere by silane coupling agent Int Nano Lett 3:1–5 doi:https://doi.org/10.1186/2228-5326-3-23
Castro CS, Garcia Júnior LCF, Assaf JM (2014) The enhanced activity of Ca/MgAl mixed oxide for transesterification. Fuel Process Technol 125:73–78. https://doi.org/10.1016/j.fuproc.2014.03.024
Chang Y-P, Chang P-H, Lee Y-T, Lee T-J, Lai Y-H, Chen S-Y (2014) Morphological and structural evolution of mesoporous calcium aluminate nanocomposites by microwave-assisted synthesis. Microporous Mesoporous Mater 183:134–142. https://doi.org/10.1016/j.micromeso.2013.09.013
da Costa Evangelista JP, Gondim AD, Souza LD, Araujo AS (2016) Alumina-supported potassium compounds as heterogeneous catalysts for biodiesel production: a review. Renew Sust Energ Rev 59:887–894. https://doi.org/10.1016/j.rser.2016.01.061
Dall'Oglio EL, PTd SJ, Oliveira PTJ, LGd V, Parizotto CA, Kuhnen CA (2014) Use of heterogeneous catalysts in methylic biodiesel production induced by microwave irradiation. Química Nova 37:411–417
Dantas J, Leal E, Mapossa AB, Cornejo DR, Costa ACFM (2017) Magnetic nanocatalysts of Ni0.5Zn0.5Fe2O4 doped with Cu and performance evaluation in transesterification reaction for biodiesel production. Fuel 191:463–471. https://doi.org/10.1016/j.fuel.2016.11.107
Dussan KJ, Cardona CA, Giraldo OH, Gutiérrez LF, Pérez VH (2010) Analysis of a reactive extraction process for biodiesel production using a lipase immobilized on magnetic nanostructures. Bioresour Technol 101:9542–9549. https://doi.org/10.1016/j.biortech.2010.07.044
Evangelista JPC, Chellappa T, Coriolano ACF, Fernandes Jr VJ, Souza LD, Araujo AS (2012) Synthesis of alumina impregnated with potassium iodide catalyst for biodiesel production from rice bran oil Fuel Process Technol 104:90–95 doi:https://doi.org/10.1016/j.fuproc.2012.04.028
Feyzi M, Norouzi L (2016) Preparation and kinetic study of magnetic Ca/Fe3O4@SiO2 nanocatalysts for biodiesel production. Renew Energy 94:579–586. https://doi.org/10.1016/j.renene.2016.03.086
Gawande MB, Goswami A, Asefa T, Guo H, Biradar AV, Peng DL, Zboril R, Varma RS (2015) Core–shell nanoparticles: synthesis and applications in catalysis and electrocatalysis. Chem Soc Rev 44:7540–7590. https://doi.org/10.1039/C5CS00343A
Ghafuri H, Rashidizadeh A, Ghorbani B, Talebi M (2015) Nano magnetic sulfated zirconia (Fe3O4@ZrO2/SO4 2−): an efficient solid acid catalyst for the green synthesis of [small alpha]-aminonitriles and imines. New J Chem 39:4821–4829. https://doi.org/10.1039/C5NJ00314H
Guo P, Huang F, Zheng M, Li W, Huang Q (2012) Magnetic solid base catalysts for the production of biodiesel. J Am Oil Chem Soc 89:925–933. https://doi.org/10.1007/s11746-011-1979-5
Hájek M, Skopal F, Čapek L, Černoch M, Kutálek P (2012) Ethanolysis of rapeseed oil by KOH as homogeneous and as heterogeneous catalyst supported on alumina and CaO. Energy 48:392–397. https://doi.org/10.1016/j.energy.2012.06.052
Hashemzehi M, Saghatoleslami N, Nayebzadeh H (2016a) Microwave-assisted solution combustion synthesis of spinel-type mixed oxides for esterification reaction. Chem Eng Commun 204:415–423. https://doi.org/10.1080/00986445.2016.1273831
Hashemzehi M, Saghatoleslami N, Nayebzadeh H (2016b) A study on the structure and catalytic performance of ZnxCu1−xAl2O4 catalysts synthesized by the solution combustion method for the esterification reaction. Comptes Rendus Chimie 19:955–962. https://doi.org/10.1016/j.crci.2016.05.006
Hojjat M, Nayebzadeh H, Khadangi-Mahrood M, Rahmani-Vahid B (2016) Optimization of process conditions for biodiesel production over CaO–Al2O3/ZrO2 catalyst using response surface methodology. Chem Pap 71:689–698. https://doi.org/10.1007/s11696-016-0096-1
Hu S, Guan Y, Wang Y, Han H (2011) Nano-magnetic catalyst KF/CaO–Fe3O4 for biodiesel production. Appl Energy 88:2685–2690. https://doi.org/10.1016/j.apenergy.2011.02.012
Komintarachat C, Chuepeng S (2009) Solid acid catalyst for biodiesel production from waste used cooking oils. Ind Eng Chem Res 48:9350–9353. https://doi.org/10.1021/ie901175d
Liu S, Ma J, Guan L, Li J, Wei W, Sun Y (2009) Mesoporous CaO–ZrO2 nano-oxides: a novel solid base with high activity and stability. Microporous Mesoporous Mater 117:466–471. https://doi.org/10.1016/j.micromeso.2008.07.026
Liu C, Lv P, Yuan Z, Yan F, Luo W (2010) The nanometer magnetic solid base catalyst for production of biodiesel. Renew Energy 35:1531–1536. https://doi.org/10.1016/j.renene.2009.10.009
Liu C-H, Huang C-C, Wang Y-W, Lee D-J, Chang J-S (2012) Biodiesel production by enzymatic transesterification catalyzed by Burkholderia lipase immobilized on hydrophobic magnetic particles. Appl Energy 100:41–46. https://doi.org/10.1016/j.apenergy.2012.05.053
Liu Q, Xin R, Li C, Xu C, Yang J (2013) Application of red mud as a basic catalyst for biodiesel production. J Environ Sci 25:823–829. https://doi.org/10.1016/S1001-0742(12)60067-9
Liu Y, Zhang P, Fan M, Jiang P (2016) Biodiesel production from soybean oil catalyzed by magnetic nanoparticle MgFe2O4@CaO. Fuel 164:314–321. https://doi.org/10.1016/j.fuel.2015.10.008
Ma G, Hu W, Pei H, Jiang L, Ji Y, Mu R (2014) Study of KOH/Al2O3 as heterogeneous catalyst for biodiesel production via in situ transesterification from microalgae. Environ Technol 36:622–627. https://doi.org/10.1080/09593330.2014.954629
Ma G, Hu W, Pei H, Jiang L, Ji Y, Mu R (2015) Study of KOH/Al2O3 as heterogeneous catalyst for biodiesel production via in situ transesterification from microalgae. Environ Technol 36:622–627. https://doi.org/10.1080/09593330.2014.954629
Macedo AL et al (2016) A mesoporous SiO2/Fe2O3/KI heterogeneous magnetic catalyst for the green synthesis of biodiesel. J Braz Chem Soc 27:2290–2299
Mandić V, Kurajica S (2015) The influence of solvents on sol–gel derived calcium aluminate. Mater Sci Semicond Process 38:306–313. https://doi.org/10.1016/j.mssp.2015.01.004
Marinkovic Milos M., I. SN, Vasic Marija B., Ljupkovic Radomir B., Rancic Sofija M., Spalovic Boban R., R. ZA (2016) Synthesis of biodiesel from sunflower oil over potassium loaded alumina as heterogeneous catalyst: the effect of process parameters Hemijska industrija 70
Mehrasbi MR, Mohammadi J, Peyda M, Mohammadi M (2017) Covalent immobilization of Candida antarctica lipase on core-shell magnetic nanoparticles for production of biodiesel from waste cooking oil. Renew Energy 101:593–602. https://doi.org/10.1016/j.renene.2016.09.022
Mutreja V, Singh S, Ali A (2011) Biodiesel from mutton fat using KOH impregnated MgO as heterogeneous catalysts. Renew Energy 36:2253–2258. https://doi.org/10.1016/j.renene.2011.01.019
Nayebzadeh H, Saghatoleslami N, Tabasizadeh M (2016) Optimization of the activity of KOH/calcium aluminate nanocatalyst for biodiesel production using response surface methodology. J Taiwan Inst Chem Eng 68:379–386. https://doi.org/10.1016/j.jtice.2016.09.041
Noiroj K, Intarapong P, Luengnaruemitchai A, Jai-In S (2009) A comparative study of KOH/Al2O3 and KOH/NaY catalysts for biodiesel production via transesterification from palm oil. Renew Energy 34:1145–1150
Rahmani Vahid B, Haghighi M (2016) Urea-nitrate combustion synthesis of MgO/MgAl2O4 nanocatalyst used in biodiesel production from sunflower oil: influence of fuel ratio on catalytic properties and performance. Energy Convers Manag 126:362–372. https://doi.org/10.1016/j.enconman.2016.07.050
Rahmani Vahid B, Saghatoleslami N, Nayebzadeh H, Maskooki A (2012) Preparation of nano-size Al-promoted sulfated zirconia and the impact of calcination temperature on its catalytic activity. Chem Biochem Eng Q 26:71–77
Shahraki H, Entezari MH, Goharshadi EK (2015) Sono-synthesis of biodiesel from soybean oil by KF/γ-Al2O3 as a nano-solid-base catalyst. Ultrason Sonochem 23:266–274. https://doi.org/10.1016/j.ultsonch.2014.09.010
Shao GN, Sheikh R, Hilonga A, Lee JE, Park Y-H, Kim HT (2013) Biodiesel production by sulfated mesoporous titania–silica catalysts synthesized by the sol–gel process from less expensive precursors. Chem Eng J 215–216:600–607. https://doi.org/10.1016/j.cej.2012.11.059
Shokuhi Rad A, Hoseini Nia M, Ardestani F, Nayebzadeh H (2016) Esterification of waste chicken fat: sulfonated MWCNT toward biodiesel production Waste and Biomass Valorization:1–9 doi:https://doi.org/10.1007/s12649-016-9732-9
Shu Q, Zhang Q, Xu G, Nawaz Z, Wang D, Wang J (2009) Synthesis of biodiesel from cottonseed oil and methanol using a carbon-based solid acid catalyst. Fuel Process Technol 90:1002–1008. https://doi.org/10.1016/j.fuproc.2009.03.007
Umdu ES, Seker E (2012) Transesterification of sunflower oil on single step sol–gel made Al2O3 supported CaO catalysts: effect of basic strength and basicity on turnover frequency. Bioresour Technol 106:178–181. https://doi.org/10.1016/j.biortech.2011.11.135
Wang P, Huang W, Zhang G, Gao Z, Tang Y, Sun K, Zhang X (2015) The facile preparation of Cu–Zn–Al oxide composite catalysts with high stability and performance for the production of dimethyl ether using modified aluminum alkoxide. J Ind Eng Chem 26:243–250. https://doi.org/10.1016/j.jiec.2014.12.001
Xie W, Peng H, Chen L (2006) Transesterification of soybean oil catalyzed by potassium loaded on alumina as a solid-base catalyst. Appl Catal A Gen 300:67–74. https://doi.org/10.1016/j.apcata.2005.10.048
Ye B, Qiu F, Sun C, Li Y, Yang D (2014) Biodiesel production from soybean oil using heterogeneous solid base catalyst. J Chem Technol Biotechnol 89:988–997. https://doi.org/10.1002/jctb.4190
Yiping Y, Zhang W, Yan L, Houfang J, CUI C-s (2015) Transesterification of soybean oil using KOH/γ-Al2O3 catalyst synthesized by sol-gel method. Paper presented at the 17th International Symposium on Relations between Homogeneous and Heterogeneous Catalysis (ISHHC17), Utrecht, Netherlands, 2015-07-12
Zhang C, Wang H, Liu F, Wang L, He H (2013) Magnetic core–shell Fe3O4@C-SO3H nanoparticle catalyst for hydrolysis of cellulose. Cellulose 20:127–134. https://doi.org/10.1007/s10570-012-9839-5
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The authors received financial support from the Ferdowsi University of Mashhad (grant number: 32390) and the Iran Nanotechnology Initiative Council (grant number: 81401).
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Kazemifard, S., Nayebzadeh, H., Saghatoleslami, N. et al. Assessment the activity of magnetic KOH/Fe3O4@Al2O3 core–shell nanocatalyst in transesterification reaction: effect of Fe/Al ratio on structural and performance. Environ Sci Pollut Res 25, 32811–32821 (2018). https://doi.org/10.1007/s11356-018-3249-7
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DOI: https://doi.org/10.1007/s11356-018-3249-7